JP6512204B2 - Lubricating paint for stainless steel plates and lubricated stainless steel plates - Google Patents

Lubricating paint for stainless steel plates and lubricated stainless steel plates Download PDF

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Publication number
JP6512204B2
JP6512204B2 JP2016216584A JP2016216584A JP6512204B2 JP 6512204 B2 JP6512204 B2 JP 6512204B2 JP 2016216584 A JP2016216584 A JP 2016216584A JP 2016216584 A JP2016216584 A JP 2016216584A JP 6512204 B2 JP6512204 B2 JP 6512204B2
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Japan
Prior art keywords
stainless steel
mass
parts
paint
lubricating
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Application number
JP2016216584A
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Japanese (ja)
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JP2017105986A (en
Inventor
淳一郎 平澤
淳一郎 平澤
孝宜 矢野
孝宜 矢野
石川　伸
伸 石川
力 上
力 上
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JFE Steel Corp
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JFE Steel Corp
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Filing date
Publication date
Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Priority to ES16870828T priority Critical patent/ES2923872T3/en
Priority to EP16870828.7A priority patent/EP3385344B1/en
Priority to CN201680070393.0A priority patent/CN108368375B/en
Priority to KR1020187015602A priority patent/KR102133799B1/en
Priority to US15/781,185 priority patent/US20180345317A1/en
Priority to PCT/JP2016/085940 priority patent/WO2017094893A1/en
Priority to MX2018006759A priority patent/MX2018006759A/en
Publication of JP2017105986A publication Critical patent/JP2017105986A/en
Application granted granted Critical
Publication of JP6512204B2 publication Critical patent/JP6512204B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/02—Natural products
    • C10M159/06—Waxes, e.g. ozocerite, ceresine, petrolatum, slack-wax
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B05D2202/15—Stainless steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/02—Sheets of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/20—Aqueous dispersion or solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2501/00—Varnish or unspecified clear coat
    • B05D2501/10—Wax
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2507/00—Polyolefins
    • B05D2507/01—Polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
    • C10M2205/143—Synthetic waxes, e.g. polythene waxes used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C10M2209/0845—Acrylate; Methacrylate used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Lubricants (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Description

本発明は、ステンレス鋼板をプレス加工する際に有用な表面潤滑性を付与する塗料、およびその塗料を塗装した潤滑ステンレス鋼板に関する。   The present invention relates to a paint that imparts surface lubricity that is useful when pressing a stainless steel sheet, and a lubricated stainless steel sheet coated with the paint.

ステンレス鋼板は一般的な軟鋼と比較して強度が高く、プレス加工時に金型からより高い面圧を受けて摺動され、鋼板表面の損傷（型かじり）が顕著となるため、鋼板表面には優れた表面潤滑性が必要である。
加工時に潤滑性を得るために一般的には潤滑油が広く用いられているが、潤滑油は垂れ落ちたり、また揮発性があり空気中に拡散するなど、作業環境を低下させる場合があった。 Stainless steel plates are higher in strength compared to common mild steels, and are subjected to sliding by receiving a higher surface pressure from the mold at the time of press processing, and damage (mold scuffing) on the surface of the steel plate becomes remarkable. Excellent surface lubricity is required.
Generally, lubricating oil is widely used to obtain lubricity at the time of processing, but the lubricating oil may drip down or become volatile and diffuse in air, which may lower the working environment. .

潤滑油以外に鋼板表面に潤滑性を付与するものとして、樹脂にワックスなどの潤滑剤を添加し焼付けにより乾燥させた固体潤滑皮膜がある。固体潤滑皮膜は、潤滑油と比較して一般的に潤滑性、耐型かじり性が優れており、皮膜自体に揮発性がないため作業環境も良好に保たれる。
ワックスは潤滑剤として広く用いられており、特に低融点のものは摩擦係数が低いために良く用いられている。しかし一方で、ワックスは固化しにくい欠点があり、ワックスを多く添加して潤滑性を向上させようとした場合、焼付け炉等で塗料を乾燥させようとしてもワックスが固化せずに皮膜にベタツキが残ってしまう問題があった。 Besides lubricating oil, there is a solid lubricating film obtained by adding a lubricant such as wax to a resin and drying it by baking, as a material that imparts lubricity to the surface of a steel sheet. Solid lubricating coatings are generally superior in lubricating properties and scuff resistance compared to lubricating oils, and the coatings themselves do not have volatility, so the working environment can be maintained well.
Waxes are widely used as lubricants, and particularly those having a low melting point are often used because of their low coefficient of friction. However, on the other hand, wax has the drawback that it is difficult to solidify, and when it is attempted to improve the lubricity by adding a large amount of wax, the wax does not solidify even when trying to dry the paint in a baking furnace etc. There was a problem of remaining.

特許文献１には、請求項１で、（ａ）特定のアクリル樹脂と、混合潤滑剤として（ｂ）金属石鹸等と（ｃ）融点Ｔｍが７０≦Ｔｍ≦１５０℃であるポリエチレン系ワックスを（ａ）の固形分に対して３〜２０ｗｔ％含む脱膜型潤滑鋼板が記載されている。この文献は（ｂ）金属石鹸等と（ｃ）特定の高融点ポリエチレン系ワックスとの混合潤滑剤を有する潤滑鋼板が深絞り性、耐カジリ性に優れるという発明を開示している。比較例７で特定の高融点ワックスのみの単独の潤滑剤の使用では耐カジリ性に劣る結果が示されている。また、比較例９、１２で、特定の高融点ワックスの配合量が２０ｗｔ％超であると鋼板との密着性に劣り、深絞り性、耐カジリ性が悪くなる（段落［００２１］、表２（その３）参照）結果が示されている。   In Patent Document 1, (a) a specific acrylic resin, (b) a metal soap as a mixed lubricant, and (c) a polyethylene wax having a melting point Tm of 70 ≦ Tm ≦ 150 ° C. A film-relief type lubricating steel sheet containing 3 to 20 wt% with respect to the solid content of a) is described. This document discloses an invention that a lubricating steel sheet having a mixed lubricant of (b) metal soap etc. and (c) a specific high melting point polyethylene-based wax is excellent in deep drawability and galling resistance. In Comparative Example 7, the use of a specific lubricant only with a high melting point wax shows a result that the resistance to galling is inferior. Further, in Comparative Examples 9 and 12, when the compounding amount of the specific high melting point wax is more than 20 wt%, the adhesion with the steel plate is inferior, and the deep drawability and the galling resistance become worse (paragraph [0021], Table 2) (See Part 3) The results are shown.

特許文献２には、特定のアクリル樹脂に、潤滑剤として融点が６０℃以上の有機固形ワックスを含有する（請求項１）加工性、耐型かじり性に優れたステンレス冷延鋼板（請求項５）が記載されている。ワックスの含有量は塗料組成物の全樹脂固形分に対して１〜１０質量％程度とする（段落［００３８］）と記載され、実施例で使用されるワックスは低融点（６８℃〜１０７℃）で、使用量はアクリル系樹脂１００質量部に対して、２．０４〜１１．１質量部で少量である。特許文献２の発明では、高融点ワックスはそれ自体の摩擦係数が高いので、摩擦係数を下げるためにはより摩擦係数が低い比較的低融点ワックスを使う、との技術的理解で開発された発明である。
特許文献２の発明は、潤滑ステンレス鋼板としての効果が得られたが、ステンレス鋼における連続プレス時や激しい深絞り成形時にはまだ改良の必要があった。 In Patent Document 2, an organic solid wax having a melting point of 60 ° C. or more is contained as a lubricant in a specific acrylic resin (Claim 1) A stainless steel cold rolled steel sheet excellent in processability and type scuff resistance (claim 5 ) Is described. The wax content is described as about 1 to 10% by mass with respect to the total resin solid content of the coating composition (paragraph [0038]), and the wax used in the examples has a low melting point (68 ° C to 107 ° C) The amount used is a small amount of 2.04 to 11.1 parts by mass with respect to 100 parts by mass of the acrylic resin. In the invention of Patent Document 2, the high melting point wax itself has a high coefficient of friction, and therefore, an invention developed with a technical understanding that a relatively low melting point wax having a lower coefficient of friction is used to lower the coefficient of friction. It is.
The invention of Patent Document 2 obtained the effect as a lubricated stainless steel plate, but still needs to be improved at the time of continuous pressing or intense deep drawing on stainless steel.

また潤滑特性向上のために融点１１５℃未満の低融点ワックスを樹脂固形分に対して２０ｗｔ％を超えて添加すると、ワックスの融点が低いため、乾燥後も塗料が固化せずにベタツキが残り、鋼板を扱う際に塗装が周辺に付着し、塗装の潤滑効果が低下する、また周辺の清掃が必要になるという問題があった。   If a low melting wax with a melting point of less than 115 ° C is added over 20 wt% relative to the resin solid content to improve lubricating properties, the wax has a low melting point, and the paint does not solidify even after drying and stickiness remains When handling a steel plate, the paint adheres to the periphery, and there is a problem that the lubricating effect of the paint is reduced, and the periphery needs to be cleaned.

特開平９−１５６０２９号公報JP-A-9-156029 特開２００８−２４８０７６号公報JP, 2008-248076, A

本発明は、上記従来技術の問題点を解決し、一般的な軟鋼より強度が高いステンレス鋼板に優れたプレス加工性を付与する潤滑塗料およびそれを用いた潤滑ステンレス鋼板を提供することを目的とする。   The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a lubricating paint which imparts excellent pressability to a stainless steel plate having higher strength than a general mild steel, and a lubricated stainless steel plate using the same. Do.

本発明者らは、前記従来技術の課題を解決するために、潤滑塗料の組成を詳細に調査した結果、特許文献２での上記の考え方に反して、意外にも、アクリル系樹脂１００質量部に対して２０質量部超の多量の高融点ワックスを使用すれば、特許文献１の混合潤滑剤を使用せず、しかも特許文献１で結果が悪かった潤滑塗料における多量の高融点ワックスの使用がステンレス鋼では特許文献２の発明の基礎となった技術的考えに反して、十分な深絞り性および耐型かじり性が得られることを知見して本発明に至った。   The present inventors investigated the composition of the lubricating paint in detail in order to solve the problems of the prior art, and as a result, contrary to the above idea in Patent Document 2, surprisingly, 100 parts by mass of acrylic resin However, if a large amount of high melting point wax exceeding 20 parts by mass is used, the use of a large amount of high melting point wax in a lubricating paint which does not use the mixed lubricant of Patent Document 1 and results in Patent Document 1 are inferior. Contrary to the technical idea that made the stainless steel steel the basis of the invention of Patent Document 2, it was found that sufficient deep drawability and scuff resistance could be obtained, and the present invention was achieved.

すなわち本発明は、以下を提供する。
（１） アクリル系樹脂およびポリエチレンワックスを含み、前記ポリエチレンワックスの融点が１１５℃以上であり、前記アクリル系樹脂１００質量部に対して２０質量部超〜５０質量部のポリエチレンワックスを含有する、ステンレス鋼板用潤滑塗料。
（２） さらに、有機カルシウム化合物を、前記アクリル系樹脂１００質量部に対して、１質量部〜１０質量部含有する（１）に記載のステンレス鋼板用潤滑塗料。
（３） 水系溶媒を用い、前記ポリエチレンワックスをエマルション化して添加する、（１）または（２）に記載のステンレス鋼板用潤滑塗料の製造方法。
（４） ステンレス鋼板上に、（１）または（２）のいずれか１に記載のステンレス鋼板用潤滑塗料を塗布し、熱風乾燥して、乾燥後の質量で片面当たり０．５〜２．５ｇ／ｍ２の潤滑皮膜を形成する潤滑ステンレス鋼板の製造方法。
（５） 上記（１）または（２）に記載のステンレス鋼板用潤滑塗料を、乾燥後の質量で片面当たり０．５〜２．５ｇ／ｍ２有する潤滑ステンレス鋼板。 That is, the present invention provides the following.
(1) A stainless steel comprising an acrylic resin and a polyethylene wax, wherein the melting point of the polyethylene wax is 115 ° C. or higher, and containing 20 to 50 parts by mass of the polyethylene wax with respect to 100 parts by mass of the acrylic resin. Lubricating paint for steel plates.
(2) The lubricating paint for stainless steel plates according to (1), further containing 1 part by mass to 10 parts by mass of an organic calcium compound with respect to 100 parts by mass of the acrylic resin.
(3) The method for producing a lubricating paint for a stainless steel sheet according to (1) or (2), wherein the polyethylene wax is emulsified and added using an aqueous solvent.
(4) On the stainless steel plate, apply the lubricating paint for stainless steel plate according to any one of (1) or (2), dry with hot air, and dry weight of 0.5 to 2.5 g per side Method of producing a lubricated stainless steel sheet for forming a lubricant film of 1 / m 2 .
(5) A lubricated stainless steel plate having the lubricating paint for a stainless steel plate according to the above (1) or (2) in a mass after drying of 0.5 to 2.5 g / m 2 per one side.

本発明の潤滑塗料を用いることにより、プレス加工性（深絞り性および耐型かじり性）に優れた潤滑ステンレス鋼板が提供される。   By using the lubricating paint of the present invention, a lubricated stainless steel sheet excellent in press-processability (deep drawability and scuff resistance) is provided.

本発明の摩擦係数および型かじり性の評価方法を説明する模式図である。BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram explaining the evaluation method of the coefficient of friction and die-sticking property of this invention.

＜ステンレス鋼板用潤滑塗料＞
本発明のステンレス鋼板用潤滑塗料は、アクリル系樹脂含有水性塗料であって、融点が１１５℃以上のポリエチレンワックスを、アクリル系樹脂１００質量部に対して２０質量部超〜５０質量部含有するステンレス鋼板用潤滑塗料である。 Lubricating paint for stainless steel plates
The lubricating paint for stainless steel plates of the present invention is an acrylic resin-containing water-based paint, which is a stainless steel containing polyethylene wax having a melting point of 115 ° C. or more, in excess of 20 parts by mass to 50 parts by mass with respect to 100 parts by mass of acrylic resin. It is a lubricating paint for steel plates.

（アクリル系樹脂）
本発明に用いるアクリル系樹脂は、特に限定されない。好ましくは１．アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸等の脂肪酸、２．上記１．の脂肪酸をメチル化、エチル化、イソプロピル化、ブチル化、２-エチルヘキシル化等をしたエステル、３．上記１．の脂肪酸とアンモニア等のアミド、４．スチレン、５．上記１．の脂肪酸にポリオキシエチレンを付加したもの、の上記１．から５．からなる群から選ばれる１種類または２種類以上をモノマーとして重合または共重合したものを使用する。重合または共重合する方法としては、溶液重合法、エマルション重合法または懸濁重合法などが例示できる。アクリル系樹脂に添加する添加剤としては、一般的に塗料に広く用いられている界面活性剤、防錆剤、極圧剤、ｐＨ調整剤等を合計で前記アクリル系樹脂１００質量部に対して１０質量部以下含有することができる。潤滑塗料の溶媒は、水系あるいは有機溶剤のいずれでも良いが水系溶媒が好ましい。 (Acrylic resin)
The acrylic resin used in the present invention is not particularly limited. Preferably 1. Fatty acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and the like; Above 1. Esters of methylated, ethylated, isopropylated, butylated, 2-ethylhexylated etc. fatty acids of Above 1. Fatty acids and amides such as ammonia; Styrene, 5. Above 1. Of the fatty acid of the present invention to which polyoxyethylene is added. To 5. What polymerized or copolymerized 1 type, or 2 or more types chosen from the group which consists of as a monomer is used. As a method of polymerizing or copolymerizing, a solution polymerization method, an emulsion polymerization method or a suspension polymerization method can be exemplified. As an additive to be added to the acrylic resin, a surfactant, an antirust agent, an extreme pressure agent, a pH adjuster and the like which are generally used widely in paints are added to 100 parts by mass of the acrylic resin in total. It can contain 10 parts by mass or less. The solvent of the lubricating paint may be either aqueous or organic, but is preferably aqueous.

（融点１１５℃以上のポリエチレンワックス）
用いるポリエチレンワックスは、融点１１５℃以上のポリエチレンワックスであれば限定されない。好ましくは中密度〜高密度ポリエチレンワックス（密度0.930g/cm3以上）を使用する。融点が１１５℃未満であると、前記アクリル系樹脂１００質量部に対して２０質量部超えて添加した場合に、塗料乾燥後に容易に固化せずにベタツキが発生するため、融点１１５℃以上のポリエチレンワックスとする。特に融点が１２０℃以上の高密度ポリエチレンワックス（密度0.942g/cm3以上）が好ましく、さらに融点が１３０℃以上のポリエチレンワックスがより好ましい。融点は１４５℃以下であることが好ましい。融点が高くなりすぎると硬くなり、プレス加工時の金型との接触で皮膜の剥離が大きくなることがある。
融点１１５℃以上のポリエチレンワックスは、エマルション化したものをアクリル系樹脂含有水性塗料に添加するとアクリル系樹脂含有水性塗料に均一に混ざり、得られる潤滑塗料の特性が優れるので好ましい。
エマルション化されたポリエチレンワックスの平均粒径は１．０μｍ未満が好ましい。平均粒径が小さいほうがポリエチレンワックスが皮膜に均一に分散するためである。さらに均一に分散するためには、平均粒径が０．２μｍ以下であればより好ましい。 (Polyethylene wax with a melting point of 115 ° C or higher)
The polyethylene wax used is not limited as long as it is a polyethylene wax having a melting point of 115 ° C. or higher. Preferably, medium density to high density polyethylene wax (density 0.930 g / cm 3 or more) is used. When the melting point is less than 115 ° C., when it is added in excess of 20 parts by mass with respect to 100 parts by mass of the acrylic resin, it is not easily solidified after paint drying and stickiness occurs, so a polyethylene having a melting point of 115 ° C. or more It will be wax. In particular, high density polyethylene wax having a melting point of 120 ° C. or more (density 0.942 g / cm 3 or more) is preferable, and polyethylene wax having a melting point of 130 ° C. or more is more preferable. The melting point is preferably 145 ° C. or less. When the melting point is too high, the film becomes hard, and the peeling of the film may be increased by the contact with the mold at the time of pressing.
A polyethylene wax having a melting point of 115 ° C. or higher is preferable because when it is emulsified, it is uniformly mixed with the acrylic resin-containing aqueous paint when added to the acrylic resin-containing aqueous paint, and the resulting lubricating paint has excellent properties.
The average particle size of the emulsified polyethylene wax is preferably less than 1.0 μm. The smaller the average particle size, the more uniformly the polyethylene wax is dispersed in the film. It is more preferable that the average particle diameter is 0.2 μm or less in order to further disperse uniformly.

添加量は、プレス加工時の面圧が高くなるステンレス鋼板に対して、前記アクリル系樹脂１００質量部に対して２０質量部超えて添加し、軟鋼の場合より多くすることが有効であることがわかった。さらに、融点が１１５℃以上で高いポリエチレンワックスは、ワックス自体の摩擦係数が高いため、添加量が前記アクリル系樹脂１００質量部に対して２０質量部以下であると、潤滑皮膜としての摩擦係数が十分に低下せず、十分な潤滑性向上効果が得られないことがわかった。一方５０質量部を超えて添加しても潤滑性向上効果は飽和する。したがって２０質量部超え〜５０質量部未満とする。樹脂固形分に対する融点１１５℃以上のポリエチレンワックスの添加量が多いほど皮膜としての摩擦係数は小さくなるが、摩擦係数が小さすぎるとコイルが自重でつぶれたり、板の持ち運びで落下させる懸念もあり、より好ましくは前記アクリル系樹脂１００質量部に対して４０質量部以下、さらに好ましくは３０質量部以下でステンレス鋼の通常のプレス加工で十分な潤滑性を得ることができる。   It is effective that the addition amount is more than 20 parts by mass with respect to 100 parts by mass of the acrylic resin with respect to the stainless steel plate where the surface pressure at the time of press processing becomes high, and larger than in the case of mild steel. all right. Furthermore, since the polyethylene wax having a high melting point of 115 ° C. or more has a high friction coefficient of the wax itself, the friction coefficient as a lubricating film is 20 parts by mass or less with respect to 100 parts by mass of the acrylic resin. It turned out that it does not fully fall and a sufficient lubricity improvement effect is not acquired. On the other hand, even if the content exceeds 50 parts by mass, the effect of improving the lubricity is saturated. Therefore, it is more than 20 parts by mass and less than 50 parts by mass. The coefficient of friction as a film decreases as the added amount of polyethylene wax with a melting point of 115 ° C or more with respect to resin solid content decreases, but if the coefficient of friction is too small, there is a concern that the coil may be crushed by its own weight or dropped by carrying the plate More preferably, sufficient lubricity can be obtained by ordinary pressing of stainless steel at 40 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the acrylic resin.

（その他の添加物）
一般的に塗料に広く用いられている界面活性剤、防錆剤、極圧剤、pH調整剤などを合計で前記アクリル系樹脂１００質量部に対して１０質量部以下含有することができる。水性塗料の溶媒は、水を主体とする溶媒で、少量の有機溶媒を含んでも良いが潤滑塗料中の揮発性有機溶剤発生量を極力低減できるので水系溶媒が好ましい。 (Other additives)
A surfactant, a rust inhibitor, an extreme pressure agent, a pH adjuster, etc. generally used widely in paints can be contained in a total amount of 10 parts by mass or less with respect to 100 parts by mass of the acrylic resin. The solvent of the water-based paint is a water-based solvent and may contain a small amount of organic solvent, but the water-based solvent is preferable because it can reduce the amount of volatile organic solvent generated in the lubricant paint as much as possible.

本発明により以下のことが初めて見出された。
１）特許文献２の基本的技術思想として、摩擦係数の小さい低融点ワックスを所定量使用する潤滑塗料では、ステンレス鋼板の高面圧のプレス加工では、前記アクリル系樹脂１００質量部に対して２０質量部以下のワックスの添加では、十分な耐型かじり性が得られない場合があり、ステンレス鋼板の高面圧のプレス加工ではより耐型かじり性を上げる必要がある。
融点１１５℃以上の高融点ポリエチレンワックスはそれ自体の摩擦係数が低融点ポリエチレンワックスよりも高いため、低融点ポリエチレンワックスと同量程度添加したのでは摩擦抵抗が十分に低下しないという懸念があったが、高融点ポリエチレンワックスを用いる場合は前記アクリル系樹脂１００質量部に対して２０質量部を超えて添加すると、アクリル樹脂の比率が低くなるため摩擦係数の高いアクリル樹脂の寄与が下がるとともに、高融点ポリエチレンワックス摩擦係数低減効果が現れるので従来得られなかった優れた潤滑性が得られる。
この理由は不明であるが以下のことが考えられる。
高融点のワックスは、低融点のワックスと比較して粘度が高く、金型と鋼板との接触摺動時にその隙間に残存しやすいため、深絞り性および型かじりに対して効果があると推定される。
２）本願の型かじり性の評価は、実施例で説明するように特許文献１，２とは異なる評価方法である。特許文献１では角筒絞りの型カジリを観察し、特許文献２ではエリクセンカップ（円筒絞り）の型カジリで評価している。評価の段階（金型と板との接触面圧）としてはおよそ、本願＞特許文献１＞特許文献２であり、本願の「同じ供試材に対して高面圧（約200MPa）で２０回連続して摺動しても摩擦係数が上昇しない」評価は、ステンレス鋼にとって好適な評価方法である。この理由はステンレス鋼では一回のプレスでは成形加工が完了せず複数回のプレス成型が行われる場合があるため、過酷なプレス成型の評価方法で初めてステンレス鋼の耐型かじり性を適切に評価できる。このような過酷なプレス成型の評価を行った従来技術はない。 The following has been found for the first time according to the invention.
1) As a basic technical idea of Patent Document 2, in the case of a lubricating paint using a predetermined amount of low melting point wax having a small coefficient of friction, 20 parts by mass of the acrylic resin is used in pressing of high surface pressure of stainless steel plate. With the addition of a wax of less than or equal to parts by weight, it may not be possible to obtain sufficient resistance to mold scuffing, and it is necessary to further improve the resistance to scuffing by high pressure surface pressing of stainless steel plates.
The high melting point polyethylene wax having a melting point of 115 ° C or higher has a concern that the friction resistance is not sufficiently lowered if the same amount as the low melting point polyethylene wax is added because the friction coefficient of itself is higher than that of the low melting point polyethylene wax In the case of using a high melting point polyethylene wax, if it is added in excess of 20 parts by mass with respect to 100 parts by mass of the acrylic resin, the ratio of the acrylic resin becomes low, so the contribution of the acrylic resin having a high friction coefficient decreases and the high melting point Since the polyethylene wax friction coefficient reducing effect appears, excellent lubricity which has not been obtained conventionally can be obtained.
Although the reason is unknown, the following can be considered.
The high melting point wax has high viscosity compared to the low melting point wax, and is likely to remain in the gap when sliding contact between the mold and the steel plate, so it is estimated that it has an effect on deep drawability and mold galling. Be done.
2) The evaluation of mold stingness of the present application is an evaluation method different from those of Patent Documents 1 and 2 as described in the examples. Patent Document 1 observes the mold burr of the square tube diaphragm, and Patent Document 2 evaluates the mold of the Erichsen cup (cylindrical diaphragm). The evaluation stage (contact surface pressure between the mold and the plate) is approximately the present application> patent document 1> patent document 2 and 20 times at a high surface pressure (about 200 MPa for the same test material of the present application) "The coefficient of friction does not increase even when sliding continuously" is a suitable evaluation method for stainless steel. The reason for this is that stainless steel may not be completely formed by a single press but may be pressed several times. Therefore, it is only necessary to properly evaluate the resistance to galling of stainless steel by the severe press forming evaluation method. it can. There is no prior art which evaluated such severe press molding.

（有機カルシウム化合物）
ステンレス鋼板のプレス成形の際には、１回のプレスでは完了せずに、複数回のプレスで成形が行われる場合がある。その際に初期のプレスで塗装が損傷を受け、その後摩擦係数が上昇して行く型かじりという現象がある。耐型かじり性を向上させるために、必要により有機カルシウム化合物を添加する。
有機カルシウム化合物は、カルシウムを６質量％以上含有しているものを使用する。例えば、ステアリン酸カルシウム、オレイン酸カルシウム，ラウリン酸カルシウム等、脂肪酸がＣ１２〜Ｃ１８の脂肪酸カルシウム。あるいは、過塩基性アルキルベンゼンスルフォン酸カルシウム、過塩基性アルキルナフタレンスルフォン酸カルシウム，過塩基性アルキルアリールスルフォン酸カルシウム等の過塩基性石油スルフォン酸カルシウムを使用する。
有機カルシウム化合物は、前記アクリル系樹脂１００質量部に対して１〜１０質量部添加すると型かじり性改善効果が得られるため、必要に応じて添加する。１質量部未満であると、型かじり性改善効果が得られない。１０質量部超えて添加しても効果は飽和する。 (Organic calcium compounds)
In the case of press forming of a stainless steel plate, the forming may be performed by a plurality of presses without being completed by one press. At that time, there is a phenomenon that the paint is damaged in the initial press, and then the coefficient of friction rises and the form of galling occurs. An organic calcium compound is added as needed to improve the resistance to galling.
As the organic calcium compound, one containing 6% by mass or more of calcium is used. For example, calcium stearate, calcium oleate, calcium laurate and the like, fatty acids of C 12 -C 18 fatty acid calcium. Alternatively, calcium overbased petroleum sulfonate such as calcium overbased alkylbenzene sulfonate, calcium overbased alkyl naphthalene sulfonate, calcium overbased alkyl aryl sulfonate, etc. is used.
The organic calcium compound is added as needed because 1 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned acrylic resin can be obtained to improve the mold stabilizability. If it is less than 1 part by mass, no effect of improving moldability can be obtained. Even if it is added in excess of 10 parts by mass, the effect is saturated.

（ステンレス鋼）
本発明のステンレス鋼板用潤滑塗料は、ステンレスの種類によらず全てのステンレス鋼板に適用でき深絞り加工性と耐型かじり性に優れる潤滑ステンレス鋼板が得られる。特に絞り加工が用いられるフェライト系ステンレス鋼板のプレス加工に適している。 (Stainless steel)
The lubricating paint for stainless steel plates of the present invention can be applied to all stainless steel plates regardless of the type of stainless steel, and a lubricated stainless steel plate excellent in deep drawability and mold scuff resistance can be obtained. In particular, it is suitable for press processing of a ferritic stainless steel sheet for which drawing processing is used.

＜潤滑ステンレス鋼板の製造方法＞
本発明のステンレス鋼板用潤滑塗料をステンレス鋼板表面に塗布して乾燥する。塗布方法は、限定されないが、スプレー塗布、ロールコーター塗布、浸漬塗布、刷毛塗塗布等の方法が例示できる。本発明塗料の固形分（アクリル系樹脂＋ポリエチレンワックス+カルシウム化合物）濃度は、用いられる塗布方法や乾燥方法に合わせて調製することができる。好ましくは１質量％〜５０質量％である。塗料の乾燥方法は、一般的な焼付け炉等を使用することが出来るが、本発明の潤滑塗料は固化しやすいため、簡易的な熱風乾燥で十分に固化させることが出来る。塗装は、鋼板の使用用途により鋼板の片面または両面に行うが、乾燥後の付着量は、片面当り０．５〜２．５ｇ／ｍ２が好ましい。
乾燥後の付着量が０．５ｇ／ｍ２〜２．５ｇ／ｍ２であると皮膜の損傷が起こりにくく、耐型かじり性が優れ、潤滑効果が十分で、摺動時の皮膜の剥がれが少なく、剥がれたものがプレス金型に堆積してプレス加工に悪影響を及ぼすことがない。より好ましくは０．８ｇ／ｍ２以上、２．０ｇ／ｍ２以下、さらに好ましくは１．５ｇ／ｍ２以下とする。 <Method of manufacturing lubricated stainless steel plate>
The lubricating paint for a stainless steel plate of the present invention is applied to the surface of a stainless steel plate and dried. Although the coating method is not limited, methods such as spray coating, roll coater coating, dip coating, brush coating can be exemplified. The solid content (acrylic resin + polyethylene wax + calcium compound) concentration of the paint of the present invention can be prepared according to the coating method and drying method to be used. Preferably, it is 1% by mass to 50% by mass. Although a general baking furnace etc. can be used for the drying method of a coating material, since it is easy to solidify the lubricating coating material of this invention, it can fully be solidified by simple hot air drying. The coating is performed on one side or both sides of the steel plate depending on the application of the steel plate, but the amount of adhesion after drying is preferably 0.5 to 2.5 g / m 2 per one side.
When the amount deposited after drying is 0.5g / m 2 ~2.5g / m 2 hardly causes damage of the film,耐型galling resistance superior lubricating effect is sufficient, peeling of the film at the time of sliding The small amount of peeling does not deposit on the press die and does not adversely affect the press working. More preferably, it is 0.8 g / m 2 or more and 2.0 g / m 2 or less, more preferably 1.5 g / m 2 or less.

（摩擦抵抗）
摩擦係数は測定方法による違いがあり、本発明で得られる潤滑皮膜の同一サンプルでも測定方法により絶対値が異なるため、絶対値では評価できないが、一般的には相対比較で高いとすべりが悪くなるため、プレス性は低下する。一方で低すぎると、鋼帯をコイルにした場合、コイルが自重でつぶれる場合があり、また滑りすぎて板のハンドリングに支障をきたす場合もある。 (Frictional resistance)
The coefficient of friction differs depending on the measurement method, and even the same sample of the lubricating coating obtained in the present invention differs in absolute value depending on the measurement method, so it can not be evaluated by the absolute value. Therefore, the pressability is reduced. On the other hand, if it is too low, when the steel strip is used as a coil, the coil may collapse due to its own weight, or it may slip too much, which may affect the handling of the plate.

以下に実施例・比較例により本発明を具体的に説明するが、本発明はこれらの実施例・比較例に限定されない。   The present invention will be specifically described by way of examples and comparative examples below, but the present invention is not limited to these examples and comparative examples.

（実施例１〜１８、比較例１〜６）
表１の組成のアクリル樹脂含有水性塗料を作製し、ステンレス鋼板（SUS444の（19mass%Cr-2mass%Mo-0.4mass%Nb）2D仕上げ）に、スプレーで均一に塗布し、ドライヤーの熱風で乾燥させる塗装を板の両面に実施し、その特性を評価した。なお、各塗料とも固形分（アクリル樹脂＋ポリエチレンワックス＋カルシウム化合物）濃度を１０質量％に調整した。その結果を表１に示す。ポリエチレンワックスはエマルション化したものを水性塗料に混合して用いた。 (Examples 1 to 18, Comparative Examples 1 to 6)
An acrylic resin-containing aqueous paint having the composition shown in Table 1 is prepared and uniformly coated by spraying on a stainless steel plate ((19 mass% Cr-2 mass% Mo-0.4 mass% Nb) 2D finish of SUS 444) and dried by hot air of a drier Paint was applied to both sides of the plate and its characteristics were evaluated. In each of the paints, the solid content (acrylic resin + polyethylene wax + calcium compound) concentration was adjusted to 10% by mass. The results are shown in Table 1. The polyethylene wax was used after being emulsified and mixed in an aqueous paint.

＜評価方法＞
１．摩擦係数は、図１に示す装置、すなわち曲率５がＲ２０の上下の金型の間に、厚さ１．５ｍｍ×長さ２００ｍｍ×幅２０ｍｍの供試材を挟み、押し付け荷重方向６で押し付けた状態で引抜荷重方向８に引抜き、引抜荷重を測定する摺動試験機で引抜荷重を測定した。摩擦係数は、引抜荷重／押し付け荷重、により求めた。試験条件は、金型：材質ＳＫＤ１１、曲率Ｒ２０、サンプル幅２０ｍｍ、摺動距離：１００ｍｍ、引抜速度：２０ｍｍ／ｓ、押し付け荷重：３９２０Ｎで行った。金型と供試材の接触面積は約２０ｍｍ２（２０ｍｍ幅×約１ｍｍ）であり、面圧は約200MPa（=3920N／20ｍｍ２）となる。
２．ベタツキ有無、潤滑皮膜形成後のステンレス鋼板に、皮膜無しのステンレス鋼を面圧0.01MPaで押し付け、剥がしたのちに皮膜無しのステンレス鋼板の表面に潤滑皮膜が転写されていないかを、蛍光Ｘ線でＣカウント量を測定することにより評価した。Ｃ量の増加は見られない場合、ベタツキ無しとした。皮膜無しのステンレス鋼板の表面にＣ量の増加があった場合をベタツキ有り、と評価した。
３．深絞り性は、限界深絞り比（ＬＤＲ（=Limiting Drawing Ratio））測定により評価した。円板形の試験片に、円筒形のポンチ（直径ｄ=33mm）を押し込み、破断することなく、絞り抜けする最大の試験片直径（Ｄ（mm））を求め、Ｄ／ｄの計算式で求めた。ポンチの肩Ｒは3mm、ポンチ送り速度1mm/秒、しわ押さえ荷重10ｋN、しわ押さえ肩Ｒ3mmで行った。
４．耐型かじり性は、図１に記載する摺動試験機を用い、１つの供試材を途中金型研磨なしで２０回連続して摺動し、摩擦係数が上昇しない場合を耐型かじり性良好と評価した。摩擦係数が上昇しないとは、「同じ供試材に対して高面圧（約200MPa）で２０回連続して摺動しても２０回目の摩擦係数が０．１５未満である」とし、この場合を耐型かじり性良好とし、「０．１５以上」を不可と評価した。 <Evaluation method>
1. The coefficient of friction is as follows: The test material of 1.5 mm thick × 200 mm long × 20 mm wide is held between the upper and lower molds of the apparatus shown in FIG. In the state, the drawing load was measured with a sliding tester which pulls out in the drawing load direction 8 and measures the drawing load. The coefficient of friction was determined by drawing load / pressing load. The test conditions were as follows: mold: material SKD11, curvature R20, sample width 20 mm, sliding distance: 100 mm, drawing speed: 20 mm / s, pressing load: 3920 N. The contact area between the mold and the test material is about 20 mm 2 (20 mm wide × about 1 mm), and the surface pressure is about 200 MPa (= 3920 N / 20 mm 2 ).
2. The stainless steel without the film is pressed against the stainless steel plate after the lubricating film formation, with a contact pressure of 0.01 MPa, peeled off, and then the fluorescent film is not transferred to the surface of the stainless steel plate without the film. It evaluated by measuring C count amount by. If no increase in the amount of C was observed, no stickiness was observed. The case where there was an increase in the amount of C on the surface of a stainless steel plate without a film was evaluated as having stickiness.
3. The deep drawability was evaluated by measuring a limiting deep drawing ratio (LDR (= Limiting Drawing Ratio)). A cylindrical punch (diameter d = 33 mm) is pressed into a disc-shaped test piece, and the maximum test piece diameter (D (mm)) to be squeezed out without breaking is obtained, and the formula of D / d is used. I asked. The punch has a shoulder R of 3 mm, a punch feed rate of 1 mm / sec, a crease pressure load of 10 kN, and a crease pressure shoulder R of 3 mm.
4. The resistance to mold galling is the resistance to galling when the friction coefficient does not increase by continuously sliding one test material 20 times without mold polishing using the sliding tester described in FIG. 1. It was evaluated as good. The fact that the coefficient of friction does not increase means that "the coefficient of friction at the 20th time is less than 0.15 even when sliding continuously 20 times with the same test material under high surface pressure (about 200 MPa)", The case was regarded as good in resistance to galling and "0.15 or more" was evaluated as unacceptable.

表１の有機カルシウム化合物の種類、
Ａ：ステアリン酸カルシウム
Ｂ：過塩基性石油スルフォン酸カルシウム
表１の樹脂の種類、
アクリル１：スチレン＋メタクリル酸ブチル＋メタクリル酸+エチレン性不飽和カルボン酸 の共重合物（質量比２５：３０：２４：２１）
アクリル２：スチレン＋メタクリル酸ブチル＋メタクリル酸 の共重合物（質量比２５：５１：２４）
表１のＰ系添加剤、
＊）オレイルアシッドホスフェイト（極圧剤） Types of organic calcium compounds in Table 1,
A: Calcium stearate B: Overbased petroleum sulfonate calcium Table 1 resin types,
Acrylic 1: Copolymer of styrene + butyl methacrylate + methacrylic acid + ethylenically unsaturated carboxylic acid (mass ratio 25: 30: 24: 21)
Acrylic 2: Copolymer of styrene + butyl methacrylate + methacrylic acid (mass ratio 25: 51: 24)
P-based additive in Table 1,
*) Oleyl acid phosphate (extreme pressure agent)

＜実施例・比較例の評価＞
表１の結果から、実施例１〜１８では、高融点のポリエチレンワックスを前記アクリル系樹脂１００質量部に対して従来の量より多い特定量添加すると、ステンレス鋼板に対して優れた加工性を有する潤滑塗料が得られることがわかる。表１の実施例１、３、５、６、１５、１７では有機カルシウム化合物を無添加としても耐型かじり性に優れるが、有機カルシウム化合物を添加するとさらに耐型かじり性が向上した。比較例１、４、６では高融点のポリエチレンワックスの量が樹脂に対して少ないと耐型かじり性が劣る。比較例５では低融点のポリエチレンワックスが前記アクリル系樹脂１００質量部に対して多量に添加されると潤滑塗料がベタツクことがわかる。比較例２，３では、低融点ワックスを使用すると、摩擦係数は低くなるがステンレス鋼用の潤滑塗料としては耐型かじり性が低いことがわかる。また、比較例１、２、３、４、６のポリエチレンワックスの添加量が低い場合、ＬＤＲ値が実施例より低く、深絞り性が劣る結果となっている。 <Evaluation of Examples and Comparative Examples>
From the results in Table 1, in Examples 1 to 18, when a specific amount larger than the conventional amount is added with respect to 100 parts by mass of the acrylic resin, the high melting point polyethylene wax has excellent processability to the stainless steel plate. It can be seen that a lubricating paint can be obtained. In Examples 1, 3, 5, 6, 15, and 17 in Table 1, the resistance to mold galling is excellent even when no organic calcium compound is added, but the addition of organic calcium compound further improves the resistance to galling. In Comparative Examples 1, 4 and 6, when the amount of the high melting point polyethylene wax is smaller than that of the resin, the mold scuff resistance is inferior. In Comparative Example 5, when a low melting point polyethylene wax is added in a large amount with respect to 100 parts by mass of the acrylic resin, it is understood that the lubricating paint is solid. In Comparative Examples 2 and 3, when the low melting point wax is used, the friction coefficient is low, but it can be seen that the lubricating paint for stainless steel has low resistance to mold scuffing. Moreover, when the addition amount of the polyethylene wax of Comparative example 1, 2, 3, 4, 6 is low, the LDR value is lower than an Example, and the result of inferior deep drawability is brought.

本発明のステンレス鋼用潤滑塗料は、ステンレス鋼板に塗布すると、深絞りや耐型かじり性等の加工性に優れる潤滑ステンレス鋼板が得られる。これを用いればステンレス鋼板を容易に高面圧のプレス成形で加工できるので、耐食性や高温特性に優れたステンレス鋼の適用が、自動車や家電、厨房分野を中心に拡大でき工業的に有用である。特にフェライト系ステンレス鋼は、Ｎｉを含有しないためオーステナイト系ステンレス鋼に比べて安価であり、しかも応力腐食割れ（ＳＣＣ）の心配がないという利点を備えているので、今後需要増加が期待される材料である。フェライト系ステンレス鋼は、軟鋼に比べてＣｒを多量に含有しているため、延性に乏しく、張り出し性に劣るため、成形可能範囲が限定されるという問題があったが、本発明のステンレス鋼用潤滑塗料を利用すれば広範囲な成型加工が可能となりその材料の特性を生かして工業製品を得ることが出来る。   When the lubricating paint for stainless steel of the present invention is applied to a stainless steel plate, a lubricated stainless steel plate excellent in workability such as deep drawing and mold scuff resistance can be obtained. Using this, it is possible to easily process stainless steel plate by high surface pressure press forming, so the application of stainless steel excellent in corrosion resistance and high temperature characteristics can be expanded mainly in the fields of automobiles, home appliances and kitchens, and is industrially useful. . In particular, ferritic stainless steels are less expensive than austenitic stainless steels because they do not contain Ni, and have the advantage that there is no concern about stress corrosion cracking (SCC). It is. Since ferritic stainless steel contains a large amount of Cr as compared to mild steel, it has a poor ductility and is inferior in stretchability, so there is a problem that the formable range is limited. By using a lubricating paint, a wide range of molding processes can be performed, and industrial properties can be obtained utilizing the characteristics of the material.

１：供試材 ２：下金型 ３：上金型 ５：曲率 ６：押し付け荷重方向
８：引抜荷重方向
1: Test material 2: Lower mold 3: Upper mold 5: Curvature 6: Pressing load direction 8: Pulling load direction

Claims (5)

アクリル系樹脂およびポリエチレンワックスを含み、前記ポリエチレンワックスの融点が１１５℃以上であり前記アクリル系樹脂１００質量部に対して２０質量部超〜５０質量部の前記ポリエチレンワックスを含有し、
さらに、有機カルシウム化合物を、前記アクリル系樹脂１００質量部に対して、１質量部〜１０質量部含有する、ステンレス鋼板用潤滑塗料。 It contains an acrylic resin and a polyethylene wax, and the melting point of the polyethylene wax is 115 ° C. or higher, and it contains more than 20 parts by mass to 50 parts by mass of the polyethylene wax with respect to 100 parts by mass of the acrylic resin .
Furthermore, the lubricating paint for stainless steel plates which contains an organic calcium compound in 1 mass part-10 mass parts with respect to 100 mass parts of said acrylic resin . 前記有機カルシウム化合物が、過塩基性石油スルフォン酸カルシウムである、請求項１に記載のステンレス鋼板用潤滑塗料。 The lubricating paint for stainless steel plates according to claim 1, wherein the organic calcium compound is calcium overbased petroleum sulfonate . 水系溶媒を用い、前記ポリエチレンワックスをエマルション化して添加する、請求項１または２に記載のステンレス鋼板用潤滑塗料の製造方法。   The method for producing a lubricating paint for stainless steel plates according to claim 1 or 2, wherein the polyethylene wax is emulsified and added using an aqueous solvent. ステンレス鋼板上に、請求項１または２に記載のステンレス鋼板用潤滑塗料を塗布し、熱風乾燥して、乾燥後の質量で片面当たり０．５〜２．５ｇ／ｍ２の潤滑皮膜を形成する潤滑ステンレス鋼板の製造方法。 The lubricating paint for a stainless steel sheet according to claim 1 or 2 is applied on a stainless steel sheet, dried with hot air, and a dry film having a weight of 0.5 to 2.5 g / m 2 per one surface is formed. Method of manufacturing a lubricated stainless steel sheet. 請求項１または２に記載のステンレス鋼板用潤滑塗料を、乾燥後の質量で片面当たり０．５〜２．５ｇ／ｍ２有する潤滑ステンレス鋼板。 A lubricated stainless steel sheet having the lubricating paint for a stainless steel sheet according to claim 1 or 2 in an amount after drying of 0.5 to 2.5 g / m 2 per one surface.
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